Insecticidal compositions



United States 2,974,083 INSECTICIDAL ooMrosrnoNs Moshe Neeman, Bulfalo,N.Y., assignor to Wisconsin Alumni Research Foundation, Madison, Wis., acorporation of Wisconsin N0 Drawing. Filed Mar. 2, 1960, Ser. No. 12,272

n Claims. Cl. 167-30) are only slightly affected by the insecticide orremain entirely unaflected by it. The need for an -improved insecticidalcomposition active against DDT resistant insects is thus evident.

To overcome the resistance of insects to DDT, it may be combined withsuitable synergists, that is, substances which potentiate theinsecticidal activity or enhance or restore the diminished or lostinsecticidial elfect of DDT on the resistant insects. The use of DDTwith potent synergists can also limit the cumulative selection of DDresistant insects in successive generations.

A number of DDT synergists have been proposed, but

they are either not suificiently potent,' or they lack the.

necessary solubility in the solvents commonly used in the commercialformulation of insecticidal compositions of DDT, such as aliphatic,naphthenic and aromatic hydrocarbons, e.'g. kerosene, decaline,tetraline,'xyl'ene, methylated naphthalenes and the like. Thus the twoCompounds hY d Nt hyH- hlorobenzenew sulfonlf-chloroanilide have beenreported to have synergistic activity with DDT, but their solubility inkerosene, decaline, xylene and similar solvents is too low to be of anypractical value for' the preparation of; insecticidal compositions inthe form of solutions or" emfilsifiable concentrates, Other proposedsynergists are objection able due to their relatively high toxicity tomen and.

2,974,083 Patented Mar 7,

are highly soluble in hydrocarbons, which makes very useful as activeingredients for the production of improved DDT-containing insecticidalcompositions}.

The product of the above formula, where R represents. 1

the ethyl group (p-chlorobenzenesulfonic acid-N-diethyl-{ amide), hasbeen described in the literature and can be made in various waysincluding the reaction of 4-.chlorobenzenesulfonyl halide with theappropriate di-alkylamine e.g. the reaction of 4-chlorobenezencsulfonylchloride with diethylamine, as described in detail below.

EXAMPLE I p-Chlorobenzenesulfonic acid-N-di-n-propylamilde One mole of4-chlorobenzene sulfonyl chloride (211 g.) and water (100 ml.) werestirred, and 111 g, of di-npropylamine (1.1 mole) was gradually addedover a period of minutes. This was followed by the gradual addition overa period of 30 minutes of an aqueous sodium hydroxide solutioncontaining44 g. of-NaQH in 440 ml. solution '(1.1 mole), while thereaction'mixture was stirred and kept at 55-60 C. by warming on a waterbath. After addition of the aqueous base, stir ring was continued for anadditional 2 /z3 hours while the temperature was kept near 60 C. Thereaction.

mixture was then cooled and the aqueous phase was drawn off from thesupernatant oily product. A small amount of amine 'and product could berecovered by mammals, and again others are difiicult and costly. to

produce therefore not easily accessible. Still others lack sufiicientchemical stability'jto be of aiiyhp'raoti'c al value in this field.

It is the object of the present invention to provide new synergists forDDT whichhave high biological'potency, are non-toxic to man, mammals andann ers easily accessible and possess adequate solubility in thesolvents commonly used for the formulation of irisctic'idalfco mpositions of DDT, along persistence in use. N

The invention comprises insecticidal DDT composij tions, containing atleast one of the compounds represented by the following formula;

in which R is an n-alkyl radical having from 2 to 7.:ca1 bon atoms.

It has been found that compounds of this type are with high chemicalstability and excellent and highly active synergists forDDT They workingup the, aqueous layer togetherwith washings of the oily layer. Theoilyproduct was washed with 2% aqueous hydrochloric acid and water, anddried over anhydrous sodium sulfate. The desired product was obtained asneedles with a melting point of 26 -27 EXAMPLE II Ipschlorobenzenasnlfqnic acid-N-di-n-burylamide One moleof4-chlorobenzcne sulfonyl chloride (211.g.) and 142 g ofdi-n-butylamine (1.1 mole) were reacted by the procedure described-inExample 1. On completion of the reaction, theproduct crystallized oncooling and was separated from the aqueous liquid by filtration. Thecrystals were triturated with 2% aqueous hydrochloric acid and water,and were filtered ed and sub sequently air-dried. The desired productafter recrystallizationfrom ethanol was obtained as prisms with amelting point of 37-375 C.

7 EXAMPLE III 'p-C'hlorobenzemzsulfonic acid-N-di-n-amylamide One moleof 3-chlorobenzenesulfonyl chloride (211 g.) i

and 173 g. of di-n-amylamine 1.1 mole) were reacted by the proceduredescribed in Example I, The desired product was obtainedas an oil with aboiling point of 156 C./0.15 mm.

EXAMPLE IV p-Chlorobenzenesulfonic acid-N-di-n-hexylamide One mole of4-chlorobenzenesulfonyl chloride (2l l g.), and 204 g. ofdi-n-hexylamine (1.1 mole) were reactedas f described in Example I. Thedesired product-was obtained as an oil with a boiling point of about C./j .0- 4 1 EXAMPLE V p-Chlorobenzenesu'lfonic acid-N-di-rt-heptylamidei211 g. of 4-chlorobenzenesulfonyl chloride (1 mole) and 234 g.of'di nheptylamine (1.1 mole) were'reacted by the procedure described inExample I. The desired 'oil witha-boiling point of v,

product was obtained as an C./0.015 mm.'-

The solubility in'kerosene of the synergists according to the ipyentionis satisfactory. The 'solubility ofthe N-diethyl compound is 11% byweight, that of the N- di-n-butyl compound 50% by weight, the other aremiscible with kerosene in all proportions. The solubility of theN-diethyl compound in xylene is about 50%, the other compounds beingmiscible in all proportions with xylene. In practice, concentratedsolutions of toxicants in xylene are used as emulsifiable concentrates,which are diluted with water before application to form insecticidalemulsions containing as a rule 20% or less of the concentrate. Highsolubility in xylene is therefore a very desirable property for asynergist.

The solubility of the compounds in other aromatic hydrocarbons issimilar to that in xylene.

In addition to being soluble in kerosene and the like, the synergisticcompounds of the present invention have the further advantage of beingcolorless, odorless and tasteless, thus causing no stains oroft-flavors, e.g. when applied to fruits or vegetables and of beingpractically innocuous to plants and warm-blooded animals. For example,no toxic eflects were observed on albino rats to which the compoundswere applied at a dose of 1 g. per kg. body weight, by stomach tube, orat 0.5 g. per kg. by intraperitoneal injection. Furthermore, the compounds are practically insoluble in water and have low vapor pressureand high boiling points, as well as high chemical stability when exposedto the influence of light, air and moisture. They have, therefore, along-lasting effect. In view of the high potency of the compositions ofthe present invention, they can be used to advantage with limitedamounts of DDT, e.g. about 23% by weight of DDT, in combination withabout 0.2-3% by weight of the potentiating agent, or mixtures of thesame, to kill undesired DDT resistant insects such as flies. The use ofrelatively low amounts of DDT is of importance as the use ofprogressively increasing amounts of DDT, in attempts to killDDT-resistant insects, has resulted in the killing of large numbers ofdesired insect species such as bees, along with the natural predators ofharmful insects. Moreover, accumulation of DDT- residues reaches levelsharmful to birds, wildlife and humans, unless the levels of DDT canagain be reduced by the use of the potentiating agents.

According to the present invention, the new synergist- DDT combinationscan be used for forming sprays for in inert, organic solvents such aspetroleum distillates of the kerosene type, solvent naphtha,hydrogenated naphthalenes, alkylated naphthalenes, chlorinatedhydrocarbons and the like; or in the form of aqueous emulsions preparedfrom emulsifiable concentrates by conventional procedures. They mayfurther be used in mixture with a conventional inert solid insecticidecarrier material which may contain a wetting or a dispersing agent. Thesynergist-DDT combinations can also be prepared in aerosol form inaccordance with conventional practices in this art.

The synergistic activity was proved by topically applying very dilutesolutions of 0.175 g. of DDT alone (as test solution), and admixed with0.0175 ,ug. of each of the synergists, respectively, in 0.175 ,ul. ofbenzene to DDT-resistant house flies. Six hours after the application,the solution of DDT alone had killed only 5% of the flies; DDT inpresence of the dipropyl product, 95%; in the presence of the diamylproduct, 85%; with similar results being obtained with the othersynergistic compounds. In similar tests with the diethyl product as thesynergist, for example, 0.1% DDT killed about 7% of the flies; 1.0%synergist, 6.5%; and a combination made up of 0.1% DDT with 0.01%synergist killed 50% of the flies.

The tables in the following two examples show results of furtherlaboratory tests demonstrating synergistic activity.

EXAMPLE VI Solutions (see Table I below) were prepared by dissolving theactive ingredients in refined kerosene, with the amount of solutes givenin parts by weight contained in 100 parts by volume of the solution.Each of the resulting solutions was dispersed during 13 seconds by meansof an atomizer to form an aerosol inside a chamber whose length, widthand height were each 1 m., at the rate of 3 ml. solution per cubicmeter. 75house flies of both sexes of a DDT-resistant strain wereexposed to the aerosol for 100 seconds while confined in a cage of wirenetting (12 mesh to the inch), which was kept swinging within the spraychamber. The percent of flies knocked down immediately after exposure,and the percent of flies dead 6 hours after exposure, were household andagricultural use in solution form dissolved recorded. Kerosene by itselfhad no effect on the flies.

Table I Effect of space sprays of the solutions on i11)1D'I resistanthouse es Dilution Parts Parts Parts of -R DDT Pyrethrtns SynergistImmediate Mortality knoek- 6 hours after down, exposure, percent percent0 0 36 23 97 8 98 22 0.5 C2H5 3 11 0.6 11-C3H1 5 10 0.5 !1C4H9 2 7 0.5Ill-05H" 4 6 0.5 n-CoHn. 2 2 0.5 n-C1Hu 3 4 0.1 01H 100 20 0.1 n-CaH- 9610 8% '8? 133 It a 11 6 Kmsen" 0.1 11-0611" 96 5 0.1 DC7H15 99 7 0.05C2115 81 78 O. 5 0. 05 11-0331 69 88 0. 5 0. 05 n-C4Hq (i7 87 0. 5 0. 05D-CgHn 53 92 0.05 DCH13 0. 5 0. 05 11-01111; 55 76 0. 5 0. 01 0. 05 CzHs100 97 0. 5 0. 01 0. 05 n-CaH1 100 0. 5 0. 01 0. 05 n-C4H0 98 61 0. 5 0.01 0.05 nC H11 99 98 0. 5 0. 01 0.05 D-CaHrs 96 59 0. 5 0. O1 0. 0511-0111" 98 79 EXAMPLE VII Deposit A was prepared by spraying uniformlya kerosene solution containing parts by weight of DDT in 100 parts byvolume of the solution onto a glass surface, at the rate of 20 ml.solution per square meter. On evaporation of the solvent, a residualdeposit of 1 g. DDT per square meter resulted.

Deposits B to F were prepared similarly, using 1(61'0'. sene solutionsof 0.5 part by weight of each of the noted synergists according to theinvention in 100' parts by volume of the solution, the residual depositsB toF of thesynergists having a surface concentration of 0.1 g.

per square meter.

DDT-resistant house filies were induced to Walk for 90 seconds over eachone of the deposits B to F, and subsequently for the same period overdeposit A. The percent of completely paralyzed flies was recorded 3hours after contact with the deposits. The results are shown in TableII. a

Table II Percent completely paralyzed flies 3 hrs.

after contact ActiveOompound First contact Second Deposit contact DDTSynergist R (G) Glass sprayed with kerosene A and dried.

(rt/m2.

In similar tests made with the diethyl product,*where 13% of the flieswere knocked downby the DDT alone and 4% by the synergist alone, aninitial contact with the synergist followed by a contact with" the. DDT,knocked down 47% of flies. r

The following tables contain illustrative data with Fowler strain DDTresistant house flies using a conventional spray or aerosol test. In theparts of Tables III-VIII marked A, the tests recorded were carried outon generations of flies highly resistant to DDT; in those marked B,flies of a lower degree of DDT-resistance were used. The test materialswere dissolved in deodorized kerosene in the concentrations, in percentweight by volume, given in the: following Tables III to VIII. In eachtest, 0.8 gal. of the test solution was discharged into a conventionalWaters vertical spraytowerthrough a glass awmizer' t 0 lb.- Pe q a e hubPr sur Th spray descended through a stainless steel cylinder of 8 inchesdiameter and 44 inches height, at the bottom of which fifty house flieswere confined in a cylindrical cage of 5 inches diameter and 2 inchesheight screened at'top and bottom. The flies were transferred afterspraying to clean cages, with access to food, and'held for 24 hours forthe observation of mortality. Each test was con- In the tables, thesynergist ducted in quadruplicate. R(C H is used to identify theproduct, p-chlorobenzenesulfonic acid-N-diethylamide; R(C H is used toidentify the product, p-chlqrobenzenesul-fonic acid-N di-n-propylamide,etc.

Table III Percent Toxlcant Percent Mortality DDT Synergist 'R(CzH5)Table, IV

Percent Toxicant Percent Mortality DDT Synergist 7 Table V PercentToxicant Percent Mortality DDT Synergist 4Hr) 2.6 Y 23.5 25.0 5.0 2.525.0 a5 0. 25 h 11.5

Table VI Percent Toxlcant Percent Mortality DDT Synergist ws u) TableVII Percent Toxlcant Percent Mortality DDT synergist mourn) Table VIIIPercent Toxicant Percent Mortality DDT Synerglst In the foregoing tests,synergistic activity has been demonstrated in the DDT compositions wherethe ratios of synergist to DDT ranges from one part of synergist toforty parts of DDT, up to ten parts of synergist to one part of DDT. Thepresent invention is thus directed in particular to insecticidal DDTcompositions for destroying insects resistant against the action of DDTalone, containing for each part of DDT, as a DDT potentiating agent,0.025-100 parts of the potentiating agent or synergist,p-chlorobenzenesulfonic -acid-N-di-(R)-amide, where R represents ann-alkyl group containing 2-7 carbon atoms. To obtain the substantialbenefits of the present invention for field use, the DDT compositionsshould contain about 0.1% or more by weight of the time tion of theinsecticidal compositions according to the present invention are, asindicated, the usual ones for pesticides, e.g. as solution or emulsionsprays, aerosols, dips (e.g. for livestock), dusting powders, watersuspensions of wettable powders, or by way of formation of residualdeposits by spraying such solutions, emulsions or suspensions ontosurfaces of the insect habitat and allowing the liquid carrier toevaporate. The dispersions, powders, solutions or emulsions may containadditional active ingredients, e.g. other insecticides such aspyrethrins, allethrin, lindane, methoxychlor, DDD (Rhothane), chlordane,aldrin, dialdrin, endrin, or organic phosphorus insecticides; acaricidessuch as benzyl benzoate or chloroalkyl-aryloXyalkyl-sulfites (e.g.aramitc); fungicides, herbicides, bactericides and the like and variouscombinations of the same. The formulations may also contain additionalingredients such as wetting, spreading, adhesive or thickening agents,emulsion stabilizers, and the like. Except for the addition of thespecified synergist or potentiating agent of the present invention, theformulations are preferably made in accordance with standard practicesin are used to prepare conventional DDT formulations. The followingexamples are illustrative.

EXAMPLE VIII Compositions A, B and C are useful as space sprays againstflying insects, including DDT-resistant house flies.

Compositions D, E and F are useful as sprays for the formation ofresidual deposits after evaporation of the solvent.

Compositions G and H are useful for spraying from aircraft onto thewater surface of the breeding places of mosquito larva.

Compositions I, J and K are useful as aerosol solutions, and are keptconfined under somewhat higher than atmospheric pressure.

Composition L is an emulsifiable concentrate mainly for agriculturaluse. On dilution with water, spontaneous emulsification takes place,with production of a very stable emulsion of high toxicity to insects.

Composition M is an emulsion concentrate useful for the preparation ofemulsions for residual sprays after dilution of one part of theconcentrate with 4 parts of water.

Compositions N and 0 are useful as emulsifiable concentrates for thepreparation of emulsion sprays by dilution with water for the protectionof livestock against mange, lice, ticks, horn flies, stable flies, andDDT-resistant house flies.

Composition P is useful as an emulsifiable concentrate for thepreparation of sprays by dilution with water for use against insectsattacking cotton.

Composition Q is an emulsifiable concentrate which after dilution withwater forms emulsions useful as delousing preparations.

Compositions R and S are useful as wettable powders, which form withwater, under negligible foaming, highly stable aqueous suspensions.

Composition T is a useful insecticidal dusting powder.

In the compositions indicated in the table below, the emulsifying and/orsurface active agents may be replaced by other suitable substanceshaving the same or similar properties, e.g. mannitan monolaurate(MNO),sodium lauryl sulfate, sodium salts of sulfonated oxidized petroleumoils, Tween (trademark), Lissapol N (trade mark) Sterox CD (trademark),Igepal CA (trademark),

synergist or potentiating agent. The modes of applica- 1 AerosolOT-(trademai-k), and the like.

Table IX Synergist Y Compo- DDT, Other Active Solid or Liquid Emulsifieror Other Ingredients Parts sition Parts Ingredients Parts Carrier, or.Solvent Parts Surface Active Parts R= Parts Agent 1. INSEOTICIDALSOLUTIONS 1 nO H 0.8 Pyrethrlns 0. 05 Refined kerosene.- 93.15

Pyrethrius 0. 08 1 nC H11. l. 2 Piperonyl 0. 7' do 97.02

. butoxide. 0.8 nCaH1 0.6 Pyrethrins 0.05 ..--.do 98.55 5 nCaH1...,. 3Li d (in 92 11 one 4 n-o.m. 2.5 {lfieghoxycmon 05 on 92.45 11 ane 4 2'{Methoxychloizu 1 hg' 5 M {rfiiiilfijifjji 42 Kern n 44.5 5 8.5 Fuel on42 Xylene 5 7 2 11-0 11".-- 1.5 Allethrln 0.6 Refined kern ne 7. 5 Freon83.4 Xylene 5 J 2 nC;H1... 0.8 Pyrethrins O. 4 Refined kerosene.. 7. 5Freon 84.3 Pyrethrlns 0. 4 Xylene 5 K 2 nC1H1 l. 5 Piperonyl 1. 0Refined kerosene- 6. 5 butoxide. Fr n 83. 6

2. INSECTIGIDAL EMULSIFIABLE OONCENTRATES 25 n-C H7.. 25 Aramite 1Xylene 44 Triton Xl77 5 25 n-C H 25 do 47.5 Triton X-lii 2,5

0 O H 22 i e e 1. 2 }Ar0matic hydro- 4s. 8 Triton X 1 7 3 2 3Methoxychlor 5 carbon. 0 11-0611,... 22 L d g n 48.8 n s 8 Triton X-1 R53 P 16 1 a 1---- 20 4 44 {Triton 13-1956.-. 5 Q 6 n-C Hu. 2 Benzylbenzoate 68 Triton X-155...- 12 Benzocainennt- 12 3. DUSTING ANDWETTABLE POWDERS n-C H 5 1 Triton X100 0.5 R j 3 }Pyrophyllite o5 {g i tg 100 5 OH 3 r on .5 S 25 {ll-03111;.-. 2 68 {Tatuol N 1.5 T 10 nC3H 3Tale 1 86. 9 Coloring agent 1 0. 1

1 The particle size of the solid carriers was between 0.5 to microns. Inthe above formulations A to T, the synerglst R= C111 was substituted forthe other synergists for uses as indicated above.

' Parathion0,0'diethyl-O"-p-nitrophenyl The products referred to by thevarious trademarks mentioned above as well as in the following examplesare as follows:

Tween 80-a polyoxyethylene derivative of sorbitan monooleate LissapolN-octylcresol poly-(C C ether alcohol Sterox CD-polyoxyethylenecondensate lgepal CA-condensate of ethylene oxide and alkylated cresolAerosol OT-dioctyl sodium sulfosuccinate Triton X-l77a blend of analkyl-aryl polyether alcohol and a modified phthalic glycerol alkydresin with emulsion stabilizer, corrosion inhibitor and foam re ducerTriton X-155-an alkyl-aryl polyether alcohol Triton X-l00an alkyl-arylpolyether alcohol Tamol N-a dispersant and stabilizer for spray mixturesLindanebenzene hexachloride containing about 99% of the gamma-isomerthiophosphate Aldrinhexachloro hexahydro dimethano-naphthalene Piperonylbutoxide-3,4-methylenedioxy-6-propylbenzyl (butyl)-diethylene glycolether.

Triton B-1956-a modified phthalic glycerol alkyd resin,

at non-ionic surface-active agent.

A practical application of combinations containing DDT together withsynergists according to the invention are illustrated in the followingexample: 1

7 EXAMPLE 1x Plywood panels were sprayed wi th a kerosene solutioncontaining 5 parts by weight of DDT and 5 parts by weight of thesynergist p-chlorobenzenesulfonic acid-N- di-n-propylamide in parts byvolume of the solution, at a rate of 20 ml. of solution per squaremeter. After drying, the residual deposit contained 1 g. of DDT and 1 g.of synergist per square meter. DDT-resistant house flies were kept incontact with the panels for 30 minutes,

when complete kill resulted. In experiments using in a like manner then-amyl synergist, or the n-heptyl synergist, complete kills of theinsects were also achieved after 30 minutes.

The present application is a continuation-in-part of my priorapplications Serial No. 574,628, filed March 29, 1956, and Serial No.617,689, filed October 23, 1956, now both abandoned.

' I claim:

1. Insecticidal DDT compositions for destroying insects resistantagainst the action of DDT alone, containing by Weightfor each part ofDDT, as a DDT potentiating agent, 0.025 to 10 parts of p-chlorobenzenesulfonic acid-N-di (R)Famide, where R represents an nalkylgroupcontaining 2 to 7 carbon atoms.

2. The composition of claim 1 where R represents the ethyl group. I

3. The composition of claim 1 where R represents the n-propyl group.

' 4. The composition of claim 1 where R represents the V f n-butylgroup.

5. The composition of'clairn l where R represents the n-amyl group.

6. The composition of claim 1 where R represents the n-hexyl group."

7. The composition of claim 1 where R represents the n-heptyl group.

8. Insecticidal spray compositions according to claim 10. Insecticidalaerosol spray compositions according to claim 1 carried in a propellant.

References Cited in the file of thispatent UNITED STATES PATENTS2,236,168 Dietrich Mar. 25, 1941 FOREIGN PATENTS 119,980 Sweden Oct. 21,1947 246,916 Sweden Nov. 1, 1947 633,136 Great Britain Dec. 19, 1951929,905 France July 22, 1947 930,527 France Aug. 11, 1947 1. OTHERREFERENCES U.S.D.A. Bull. E-775, April 1949, pp. 1-51; Pp. 1 and 20pert.

Sumerford: J. of Agr. and Food Chem., vol. 2, No. 6, Mar. 17, 1954, pp.310-327 (pp. 318, 320 relied on).

Nature, vol. 177, Apr. 28, 1956, page 800.

Wadley: The Evidence Required to Show Synergistic Action of Insecticidesand a Short Cut in Analysis,

U.S.D.A., June 1945, pp. 1-7.

Hackh: Chem. Dictionary, 3rd ed., The Blakiston Co. (1944), p. 4.

Frear: Chem. of Insecticides, Fungicides and Herbicides, 2nd ed., 1948,D. Van Nostrand, pp. 62-63, 67, 68,

King: U.S.D.A. Handbook No. 69, May 1954, pp. 67, 68.

. UNITED STATESPATENT OFFICE CERTIFICATE 0 CORRECTION Patent No u 2 974O88 March 7 1961 Moshe Neeman It is hereby certified that error appearsin the above numbered patent requiring correction andthat the saidLetters Patent should read as corrected below Column 2 line 54 for Or,15" read 0,015 column 3, line 31 for "O.,2=-3%" read Oo2-O.3% column 4,TABLE I, second column thereof, lines 17 and 21, strike out the leadersand insert, instead 0.5 "-3 c0lumn 8 line 23, for "are" read art eSigned and sealed this 10th day Of October 1961c (SEAL) Attest:

ERNEST W. sWIDER DAVID L. LADD Attesting Officer Commissioner of PatentsUSCOMM-DC

1. INSECTICIDAL DDT COMPOSITION FOR DESTROYING INSECTS RESISTANT AGAINSTTHE ACTION OF DDT ALONE, CONTAINING BY WEIGHT FOR EACH PART OF DDT, AS ADDT POTENTIATING AGENT 0.025 TO 10 PARTS OF P-CHLOROBENZENESULFONICACID-N-DI(R)-AMIDE, WHERE R REPRESENTS AN NALKYL GROUP CONTAINING 2 TO 7CARBON ATOMS.